EP0514172B1 - Film soluble dans l'eau - Google Patents

Film soluble dans l'eau Download PDF

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Publication number
EP0514172B1
EP0514172B1 EP92304350A EP92304350A EP0514172B1 EP 0514172 B1 EP0514172 B1 EP 0514172B1 EP 92304350 A EP92304350 A EP 92304350A EP 92304350 A EP92304350 A EP 92304350A EP 0514172 B1 EP0514172 B1 EP 0514172B1
Authority
EP
European Patent Office
Prior art keywords
film
polyvinyl alcohol
hydrolyzed polyvinyl
acrylate copolymer
material selected
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92304350A
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German (de)
English (en)
Other versions
EP0514172A1 (fr
Inventor
Andrew Vanputte
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cryovac LLC
Original Assignee
WR Grace and Co Conn
WR Grace and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by WR Grace and Co Conn, WR Grace and Co filed Critical WR Grace and Co Conn
Publication of EP0514172A1 publication Critical patent/EP0514172A1/fr
Application granted granted Critical
Publication of EP0514172B1 publication Critical patent/EP0514172B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7166—Water-soluble, water-dispersible
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2553/00—Packaging equipment or accessories not otherwise provided for
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334—Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1341—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1379—Contains vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit
    • Y10T428/1383—Vapor or gas barrier, polymer derived from vinyl chloride or vinylidene chloride, or polymer containing a vinyl alcohol unit is sandwiched between layers [continuous layer]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31909—Next to second addition polymer from unsaturated monomers
    • Y10T428/31928—Ester, halide or nitrile of addition polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/31935—Ester, halide or nitrile of addition polymer

Definitions

  • the present invention relates to polymeric film, and more particularly to water soluble film suitable for packaging caustic materials.
  • EP-A-0 457 600 discloses a water-soluble film comprising an outer layer, which comprises a water-soluble polymeric material, an intermediate layer comprising a material providing tensile strength, bulk or abuse resistance to the film and an innter layer, which comprises a polymeric material compatible with the contents of a package formed from the film.
  • the inner layer may comprise an acid/acrylate copolymer, styrene-maleic anhydride copolymer, ethylene acrylic acid copolymer, ionomer, such as a metal salt neutralized ethylene methacrylic acid copolymer in which the acid content is at least about 20 mol-%, vinyl acrylate copolymer, cellulose, hydroxy propyl cellulose, polyether block amide copolymer, polyhydroxy butyric acid, polyhydroxy valeric acid, polyethylene oxide, polyester, copolyester, polyethoxazoline or polyurethane.
  • an acid/acrylate copolymer styrene-maleic anhydride copolymer
  • ethylene acrylic acid copolymer such as a metal salt neutralized ethylene methacrylic acid copolymer in which the acid content is at least about 20 mol-%
  • vinyl acrylate copolymer cellulose, hydroxy propyl cellulose, polyether block amide copolymer
  • the present invention provides a multilayer film which can effectively and efficiently store a quantity of a chemical, including caustic chemicals, and avoid the need of the end user to open a container to create access to the chemical material.
  • a water soluble film comprises an outer layer comprising a material selected from fully hydrolyzed polyvinyl alcohol, partially hydrolyzed polyvinyl alcohol, and polyethylene oxide; an intermediate layer comprising a material selected from fully hydrolyzed polyvinyl alcohol, partially hydrolyzed polyvinyl alcohol, and polyethylene oxide; and an inner layer comprising a material selected from partially metal salt neutralized acid/acrylate copolymer, and a blend of acid/acrylate copolymer and ionomer.
  • a method for coextruding a packaging film comprises the steps of simultaneously extruding an outer layer comprising a material selected from fully hydrolyzed polyvinyl alcohol, partially hydrolyzed polyvinyl alcohol, and polyethylene oxide, an intermediate layer comprising a material selected from fully hydrolyzed polyvinyl alcohol, partially hydrolyzed polyvinyl alcohol, and polyethylene oxide, and an inner layer comprising a material selected from partially metal salt neutralized acid/acrylate copolymer, and a blend of- acid/acrylate copolymer and ionomer; joining the layers together at an annular coextrusion die; and hot blowing the coextrudate to make the packaging film.
  • the materials just described are simutaneously extruded; joined together at a sheet coextrusion die; and cast to make the packaging film.
  • a water soluble film 10 includes an outer layer 12 of a water soluble polymeric material.
  • This outer layer 12 may be a fully hydrolyzed polyvinyl alcohol (PVA) such as Vinex 1003 available from Air Products.
  • PVA polyvinyl alcohol
  • a feature of the fully hydrolyzed PVA of outer layer 12 is that it is insoluble in cold water but increasingly soluble in water at higher temperatures. Typically, at water temperatures above about 120°F fully hydrolyzed PVA such as the Vinex 1003 resin is fully soluble in water.
  • Outer layer 12 may also be a low melting point, water soluble coating.
  • low melting point is meant a melting point of between about 120 and 180°F, more preferably between about 130 and 170°F, even more preferably between about 140 and 160°F, and most preferably about 150°F.
  • Inner layer 16 includes a polymeric material which is compatible with the contents of a package made from the film.
  • Layer 16 normally will be the innermost layer of a package formed from the film and therefore will be in contact with the caustic chemical, pesticide, fertilizer, etc. which is packaged.
  • the term "caustic” is used herein to mean a chemical or mixture of chemicals with a pH of 7.0 or higher, i.e. alkaline.
  • compatible with is meant that the composition of inner layer 16 is such that during normal storage and use, the material of layer 16 will not appreciably decompose or degrade as a result of contact with the package contents. Instead, the material of layer 16 will dissolve when the contents of the container are exposed to water.
  • These contents can include highly caustic chemicals and detergents, pesticides, fertilizers, soaps, and other materials which can aggressively attack some packaging materials.
  • Layer 16 is made of a partially metal salt neutralized acid/acrylate copolymer preferably methacrylic acid/ethyl acrylate copolymer such as that available from Belland as GBC 2580 and 2600; and a blend of acid/acrylate copolymer and ionomer.
  • Non-polymeric materials such as aluminum may be coated or sputtered onto the water-soluble layer 12.
  • Layer 14 is used in the inventive laminate.
  • Intermediate layer 14 includes a polymeric material which contributes to the tensile strength of the overall water soluble film.
  • An especially preferred polymeric material for layer 14 is a partially hydrolyzed PVA such as Vinex 2034 available from Air Products.
  • Preferred partially hydrolyzed PVA materials have a degree of hydrolysis of preferably at least about 60%, and more preferably at least about 70%. Most preferably, such partially hydrolyzed PVA materials are hydrolyzed at between 85 and 98% hydrolysis. Such partially hydrolyzed PVA materials are soluble in both cold and hot water.
  • An alternative material also suitable for intermediate layer 14 is Polyethylene oxide, such as that available from Union Carbide as Poly Ox WSR.
  • Layer 14 can contribute to the tensile strength of the overall film, but also to such properties as bulk, abuse resistance, and the like.
  • Vinex 1003 A fully hydrolyzed polyvinyl alcohol (Vinex 1003) was coextruded with a partially hydrolyzed polyvinyl alcohol (Vinex 2034), and a methacrylic acid/ethyl acrylate copolymer (Belland GBC 2580).
  • the annular coextrusion die was set at 400 to 410°F.
  • the Vinex 1003 ran at a temperature of about 360 to 400°F (extrusion temperature).
  • the Vinex 2034 resin ran at a temperature of about 375 to 420°F.
  • the Belland GBC 2580 ran at a temperature of about 320 to 360°F.
  • the film of Example 1 had a total thickness of about 4.0 mils, with the outer layer of fully hydrolyzed PVA comprising about 1 mil; the intermediate layer of partially hydrolyzed PVA comprising about 2 mils; and the inner contents-compatible layer having a thickness of about 1 mil.
  • a film like that of Example 1 is made, but including a water soluble filler in the inner layer.
  • the film of the present invention is preferably carried out by coextrusion techniques well known in the art, resins which are not suitable for coextrusion processes may be brought together by extrusion coating or conventional lamination techniques to produce the final water soluble film. Both discrete layers and coatings can be used for any of the layers of the inventive laminate.
  • water soluble refers to a film structure which is preferably totally water soluble. However, films which are substantially water soluble but have relatively minor amounts of a material in the film structure which is not water soluble; films with materials which are water soluble only at relatively high water temperatures or only under limited pH conditions; and films which include a relatively thin layer of water insoluble material, are all included in the term "water soluble”.
  • the film of the present invention offers several advantages.
  • the user does not have to open the package and therefore is not exposed to potentially hazardous contents.
  • the conventional container is not recyclable and therefore can pose a hazard to the environment from residual contents within the container.
  • the present invention offers a water soluble film which can be formed into a biodegradable package which can be used as is, with the appropriate contents within the package, and without the need for attempting to recycle a container.
  • packages can contain premeasured portions so that no measuring is required and the package can be used as is.
  • the water soluble layer 12 of film 10 preferably is soluble only at relatively high water temperatures, other "triggering" mechanisms may be employed.
  • some resin materials may be water soluble at certain ranges of pH.
  • resins such as the SMA and EAA or EMAA resins can be incorporated into the film structure at relatively low pH conditions, and thereafter formed into a container which is used in a high pH environment where the water soluble layer will decompose.
  • the film may be protected from accidental failure (i.e. weakening or dissolving by water) by enclosing the package inside an overwrap material.
  • overwrap materials in the form of bags, pouches or the like are well known in the art and are typically made up of polyolefin monolayer or multilayer films or laminates. These overwrap materials can also be made from paper, metal, and substances besides synthetic polymers.
  • these films can become tacky over time.
  • Second, the rate of dissolution of the film can be slower than desired.
  • These problems can be overcome to some extent by adding a water soluble filler to one or more resins making up the film. This is preferably done by compounding the agent as a powder into the base resin prior to or during extrusion.
  • Such fillers can solve the tackiness problem by acting as an antiblock, which reduces blocking and improves processing and converting operations.
  • Such fillers can also dissolve quickly, promoting dispersion of the polymer. This in turn increases the surface area of the material, speeding up dissolution.
  • these fillers can also function as a pigment.
  • Water soluble fillers meeting one or more of these properties are included in the base resin preferably in a masterbatch or "fully let down” form.
  • the fillers are preferably of sufficiently small particle size for conversion to film. A particle size of about 5 microns or less is preferred.
  • the water soluble fillers can be compounded into the base resin on conventional compounding equipment such as a twin screw.
  • Stainless steel cooling belts can be used, instead of water, to cool and/or quench the resulting stands.
  • Such belts are commercially available from Sandvik and Berndorf.
  • the compounded resin can then be used in conventional extrusion operations to produce water soluble film.
  • Suitable water soluble fillers include any material which is water soluble, or substantially so, and capable of being incorporated into the film structures disclosed in this specification.
  • Preferred materials are salts, and more preferably alkali or alkaline earth salts such as sodium carbonate (Na 2 CO 3 ); sodium sulfate (Na 2 SO 4 ); sodium chloride (NaCl); potassium carbonate (K 2 CO 3 ); potassium sulfate (K 2 SO 4 ); and potassium chloride (KCl).
  • water soluble fillers can be included in one or more of the layers of the water soluble film of the invention.
  • the filler can be present in any suitable concentration in a given layer. Optimal concentrations will be governed to some extent by the nature of the filler, the nature of the base resin, the specific end use of the film, processing and packaging equipment, and other factors.
  • a preferred concentration of the filler or fillers for a given layer of the film is between about 100 parts per million (.01%) and 200,000 parts per million (20%) by total weight of the layer.
  • the inventor When using the acid/acrylate copolymer such as the Belland GBC material described above, the inventor has found that these resins process at relatively low temperatures, on the order of 300°F. This temperature is considerably lower than that of many of the resins mentioned above, and which are preferably for use in a multilayer coextruded structure. In addition, the viscosity of these resins is highly temperature dependent. These materials get very fluid at the desired temperatures for coextrusion. The acid/acrylate copolymer also has very low melt strength, and is very tacky and sticky. It is therefore a difficult material to process into a coextruded blown film.
  • the material is partially neutralized. This can be done by adding a base such as sodium hydroxide to the resin, in a melt reaction. Generally, alkali metal bases, and those having zinc as a metal, are preferred.
  • a base such as sodium hydroxide
  • alkali metal bases and those having zinc as a metal, are preferred.
  • An alternative is to blend an ionomer, such as commercially available ionomers, with the resin. In either case, an ionically cross-linked material results. It is characterized by more favorable rheology for coextrusion processes; much higher melt strength; less tackiness; better compatibility with the other resins used in the coextrusion process; and little or no adverse effect on the water solubility of the film.

Landscapes

  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Jellies, Jams, And Syrups (AREA)
  • Cosmetics (AREA)
  • Wrappers (AREA)

Claims (12)

  1. Film hydrosoluble coextrudé comprenant :
    (a) une couche externe comprenant un matériau choisi parmi les alcools polyvinyliques totalement hydrolysés, alcools polyvinyliques partiellement hydrolysés et oxydes de polyéthylène.
    (b) une couche intermédiaire comprenant un matériau choisi parmi les alcools polyvinyliques totalement hydrolysés, alcools polyvinyliques partiellement hydrolysés et oxydes de polyéthylène ; et
    (c) une couche interne comprenant un matériau choisi parmi des copolyméres acrylates/acide partiellement neutralisé par un sel métallique et un mélange de copolymère acrylate/acide et d'ionomère.
  2. Film selon la revendication 1 caractérisé en ce que le film comprend une charge dans au moins l'une des couches du film.
  3. Film selon la revendication 2 caractérisé en ce que la charge est un sel.
  4. Film selon la revendication 3 caractérisé en ce que le sel est un sel alcalin ou alcalino terreux.
  5. Film selon la revendication 3 ou 4 caractérisé en ce que le sel est sélectionné parmi les carbonates de sodium (Na2CO3) ; sulfate de sodium (Na2SO4) ; chlorure de sodium (NaCl) ; carbonate de potassium (K2CO3) ; sulfate de potassium (K2SO4) et chlorure de potassium (KCl)
  6. Film selon la revendication 3, 4 ou 5 caractérisé en ce que le sel comprend 1 000 parties par million (0,1 %) à 200 000 parties par million (20 %) en poids total d'au moins une des couches du film.
  7. Procédé pour la coextrusion d'un film hydrosoluble selon la revendication 1 comprenant :
    (a) la coextrusion simultanée d'une couche externe comprenant un matériau choisi parmi les alcools polyvinyliques totalement hydrolysés, alcools polyvinyliques partiellement hydrolysés et oxydes de polyéthylène,
       d'une couche intermédiaire comprenant un matériau choisi parmi les alcools polyvinyliques totalement hydrolysés, alcools polyvinyliques partiellement hydrolysés et oxydes de polyéthylène et
       d'une couche interne comprenant un matériau choisi parmi un copolymère acrylate/acide partiellement neutralisé par un sel métallique et un mélange de copolymère acrylate/acide et d'ionomère ;
    (b) l'assemblage des couches entre elles dans une filière annulaire de coextrusion et
    (c) le soufflage à chaud du coextrudat pour obtenir le film d'emballage.
  8. Procédé pour la coextrusion d'un film hydrosoluble selon la revendication 1 qui comprend les étapes consistant à
    (a) extruder simultanément une couche externe comprenant un matériau choisi parmi les alcools polyvinyliques totalement hydrolysés, alcools polyvinyliques partiellement hydrolysés et oxydes de polyéthylène,
       une couche intermédiaire comprenant un matériau choisi parmi les alcools polyvinyliques totalement hydrolysés, alcools polyvinyliques partiellement hydrolysés et oxydes de polyéthylène et
       une couche interne comprenant un matériau choisi parmi les copolymères acrylate/acide partiellement neutralisé avec des sels métalliques et un mélange de copolymère acrylate/acide et d'ionomère ;
    (b) assembler les couches entre elles à l'aide d'une filière pour feuilles de coextrusion ;
    (c) mouler le coextrudat pour obtenir le film d'emballage.
  9. Procédé selon la revendication 7 ou 8 comprenant en outre l'étape de mélange d'une charge avec au moins l'un des matériaux préalablement à, ou simultanément avec la coextrusion des couches externe, intermédiaire et interne.
  10. Procédé selon la revendication 7, 8 ou 9 comprenant en outre l'étape de mélange de 1.000 parties par million (0,1 %) à 200.000 parties par million (20 %) d'une charge avec au moins l'un des matériaux préalablement à, ou simultanément avec la coextrusion des couches externe, intermédiaire et interne.
  11. Procédé selon l'une quelconque des revendications 7 à 10 comprenant en outre l'étape préliminaire, consistant à faire réagir à l'état fondu un copolymère acrylate/acide et une base pour former l'ionomère partiellement neutralisé avec un sel métallique.
  12. Procédé selon l'une quelconque des revendications 7 à 11 comprenant en outre l'étape préliminaire consistant à mélanger un copolymère acrylate/acide et un ionomère.
EP92304350A 1991-05-14 1992-05-14 Film soluble dans l'eau Expired - Lifetime EP0514172B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US70001491A 1991-05-14 1991-05-14
US700014 1991-05-14

Publications (2)

Publication Number Publication Date
EP0514172A1 EP0514172A1 (fr) 1992-11-19
EP0514172B1 true EP0514172B1 (fr) 1998-04-15

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ID=24811861

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92304350A Expired - Lifetime EP0514172B1 (fr) 1991-05-14 1992-05-14 Film soluble dans l'eau

Country Status (8)

Country Link
US (1) US5429874A (fr)
EP (1) EP0514172B1 (fr)
AT (1) ATE165044T1 (fr)
AU (1) AU655259B2 (fr)
CA (1) CA2068269C (fr)
DE (1) DE69225087T2 (fr)
NZ (1) NZ242597A (fr)
ZA (1) ZA923247B (fr)

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DE69225087T2 (de) 1998-11-19
ATE165044T1 (de) 1998-05-15
CA2068269A1 (fr) 1992-11-15
AU655259B2 (en) 1994-12-08
NZ242597A (en) 1995-07-26
DE69225087D1 (de) 1998-05-20
AU1606992A (en) 1992-11-19
ZA923247B (en) 1993-01-27
US5429874A (en) 1995-07-04
EP0514172A1 (fr) 1992-11-19

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